(a) Reaction rates (i) Following the course of a reaction Reactions can be followed by measuring changes in concentration, mass and volume of reactants or products.

g

Measuring a change in mass Measuring a change in volume Mass of beaker and contents reactants ishighestat thispoint. rateThe ishighest atstart the reaction concentrationbecause ofthe of The steepnessThe (gradient) plotted of the indicates line ratethe the reaction. of Time

Volume of gas produced Time We can also measure changes in product concentration using a pH meter for reactions involving acids or alkalis, or by taking small samples and analysing them by titration or

spectrophotometry. Concentration

reactant

Time Calculating the average rate

The average rate of a reaction, or stage in a reaction, can be calculated from initial and final quantities and the time interval.

change in measured factor Average rate = change in time

Units of rate The unit of rate is simply the unit in which the quantity of substance is measured divided by the unit of time used. Using the accepted notation, ‘divided by’ is represented by unit-1. For example, a change in volume measured in cm3 over a time measured in minutes would give a rate with the units cm3min-1. 0.05-0.00 Rate =

50-0

1 - 0.05 = 50

= 0.001moll-1s-1 Concentration moll Concentration

0.075-0.05 Rate = 100-50

0.025 = 50 = 0.0005moll-1s-1 The rate of a reaction, or stage in a reaction, is proportional to the reciprocal of the time taken.

1 Rate  Rate is inversely proportional to time. time

i.e. 1 and 1 Rate = Time = time rate

Units: s-1, min-1 etc. Units: s, min etc.

See Unit 1 PPA 1 and Unit 1 PPA 2 for examples of ‘clock reactions’ that use the relationship described above. (ii) Factors affecting rate The rates of reactions are affected by changes in concentration, particle size and temperature.

The rate of reaction can be increased by - decreasing the particle size of a solid reactant - increasing the concentration of a reactant in solution - increasing the temperature at which the reaction occurs.

The factors which affect reaction rate can be understood more fully by examining the conditions needed for a reaction to take place. For a chemical reaction to occur, reactant particles must collide – this is the basis for the Collision theory.

The collision theory can be used to explain the effects of concentration and surface area on reaction rates. Collision Theory

For a chemical reaction to occur reactants must come into contact (collide).

Not all collisions are successful. There are two conditions that are required for a successful collision; (i) The correct collision geometry i.e. reactants must collide with a particular orientation.

(ii) Enough energy to break existing bonds within the reactant molecules.

The first condition above can be used to help explain the affect of changing the concentration or the particle size.

Any factor which increases the number of collisions per second between particles of reactants is likely to increase the rate of reaction. For many reactions a graph of rate against concentration is a straight line showing Rate that the rate is directly proportional to concentration.

Concentration The Effect of Temperature on the Rate of Reaction

We discovered that the rate of reaction is not directly proportional to the temperature, instead a 10°C rise in temperature roughly doubles the rate. Rate

The increase in the number of collisions at a higher temperature is not enough on its own to account for this increase in the rate. Temperature Activation Energy and Energy Distribution The activation energy is the minimum kinetic energy required by colliding particles before reaction will occur.

Unsuccessful collision:

reactants collide not enough reactants energy to move apart break bonds Successful collision:

reactants enough collide energy to products break bonds move apart ≥ Activation energy Temperature is a measure of the average kinetic energy of the particles of a substance.

Energy distribution diagrams can be used to explain the effect of changing temperature on the kinetic energy of particles.

T1 T2

The shaded areas represent the total number of molecules which have sufficient energy to react. The effect of temperature on reaction rate can be explained in terms of an increase in the number of particles with energy greater than the activation energy.

T1 T2

T2>T1

A small rise in temperature causes a significant increase in the number of molecules which have energy greater than the activation energy. Enthalpy

Potential energy diagrams

Exothermic changes cause heat to be released to the surroundings.

During an exothermic reaction potential energy possessed by the reactants is released to the surroundings. The products have less potential energy than the reactants. Endothermic changes cause absorption of heat from the surroundings.

In an endothermic reaction the reactants absorb energy from the surroundings so that the products possess more energy than the reactants. The enthalpy change is the energy difference between the reactants and the products.

The enthalpy change can be calculated from a potential energy diagram (if drawn to scale).

The enthalpy change has a negative value for exothermic reactions. The enthalpy change has a positive value for endothermic reactions.

Enthalpy changes are usually quoted in kJmol-1. A potential energy diagram can be used to show the energy pathway for a reaction.

products The activated complex is an unstable arrangement of atoms formed at the maximum of the potential energy barrier, during a reaction. If the total energy change for the bond breaking step is less than for the bond making step, the overall reaction will be exothermic. If the reverse is true then the reaction will be endothermic. The activation energy is the energy required by colliding molecules to form an activated complex.

In potential energy diagrams the activation energy appears as an ‘energy barrier’. The rate of a reaction will depend on the height of this barrier. The higher the barrier the slower the reaction. Note: the rate of reaction does not depend on the enthalpy change.

The activation energy can be calculated from potential energy diagrams (if drawn to scale). (iv) Catalysts

A catalyst is a substance which alters the rate of a reaction without being used up in the reaction.

Catalysts can be classified as either heterogeneous or homogeneous. Heterogeneous – catalyst is in a different physical state from the reactants. Homogeneous – catalyst is in the same physical state as the reactants.

Catalysts are used in many industrial processes.

Catalyst Process Reaction Manufacture Revisited in

Vanadium(V) oxide Contact 2SO2 + O2 2SO3 sulphuric acid

Iron Haber N2 + 3H2 2NH3 ammonia Unit 3

Platinum Ostwald 4NH3 + 5O2 4NO + 6H2O nitric acid

Nickel Hydrogenation Unsaturated oils + H2  margarine Unit 2 saturated fats Aluminium silicate Catalytic Breaking down long-chain fuels and Unit 2 cracking hydrocarbon molecules monomers for plastics industry Heterogeneous catalysts work by the adsorption of reactant molecules.

The surface activity of a catalyst can be reduced by poisoning if certain substances are preferentially adsorbed or even permanently attached to the surface of the catalyst.

Impurities in the reactants result in the industrial catalysts having to be regenerated or renewed. Catalytic convertors are fitted to cars to catalyse the conversion of poisonous carbon monoxide and oxides of nitrogen to carbon dioxide and nitrogen.

The convertors contain honeycomb ceramic material covered with a metal catalyst such as platinum or rhodium.

The honeycomb structure is used to increase the surface area of the catalytic convertor.

Cars with catalytic converters only use ‘lead-free’ petrol to prevent poisoning of the catalyst. Enzymes Enzymes catalyse the chemical reactions which take place in the living cells of plants and animals.

For example, amylase catalyses the hydrolysis of starch and catalase catalyses the decomposition of hydrogen peroxide in the blood.

Enzymes are usually highly specific. The molecular shape of an enzyme usually plays a vital role in its function.

substrate Products

enzyme Enzymes operate most effectively at a certain optimum temperature and within a narrow pH range.

Above this temperature or outwith this pH range the enzyme changes shape (the lock and key no longer fit together) and the enzyme is denatured.

Enzymes are used in many industrial processes.